EP1379708B1 - Poudre de revetement a base de sous-oxydes de titane chimiquement modifies - Google Patents

Poudre de revetement a base de sous-oxydes de titane chimiquement modifies Download PDF

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Publication number
EP1379708B1
EP1379708B1 EP02740417A EP02740417A EP1379708B1 EP 1379708 B1 EP1379708 B1 EP 1379708B1 EP 02740417 A EP02740417 A EP 02740417A EP 02740417 A EP02740417 A EP 02740417A EP 1379708 B1 EP1379708 B1 EP 1379708B1
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EP
European Patent Office
Prior art keywords
coating powder
coating
powder according
powder
sub
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02740417A
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German (de)
English (en)
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EP1379708A2 (fr
Inventor
Lutz-Michael Berger
Sven Thiele
Manfred Nebelung
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides

Definitions

  • the invention relates to coating powders based on chemically modified suboxides of titanium having the general formula Ti n-2 Me 2 O 2n-1 , wherein Me is Cr or V, for use in various coating technologies (such as the different variants of thermal spraying such as plasma spraying, high velocity flame spraying (HVOF) and detonation spraying, and other processes such as laser coating).
  • thermal spraying such as plasma spraying, high velocity flame spraying (HVOF) and detonation spraying, and other processes such as laser coating.
  • the coating powder according to the invention can be applied to various components.
  • the layers are characterized by high electrical conductivity and solid lubricant properties.
  • application possibilities for the components coated with the powder according to the invention are derived as a functional layer for fuel cells, in electrochemical plants, in vehicle construction, in mechanical engineering, and in other economic sectors.
  • Coating powders based on titanium suboxides in addition to a detailed representation of the prior art in DE 100 00 979 (to avoid unnecessary repetition, reference is made to this representation only). These powders are characterized in that n in the formula Ti n O 2n-1 has a narrow range of n ⁇ 2 or narrower and the coating powder particles have a particle size in the range 10-90 microns. In coating experiments, however, it was found that the layers sprayed from this powder had an oxygen deficit compared to TiO 2 , but a disturbing partial oxidation during the coating process is unavoidable.
  • the coating powders according to the invention are modified by at least one metallic alloying element and can be described by the general formula Ti n-2 Me 2 O 2n-1 , where Me is Cr or V and the coating powder is a grain size in the range of 10-90 microns.
  • the coating powders contain one or more further alloying elements which stabilize or are inert to individual phases of the general formula Ti n-2 Me 2 O 2n-1 .
  • Titanium suboxides with planar defect structures can also be described as homologous series with the formula x TiO 2 * Ti 2 O 3 . They can be located next to the in DE 100 00 979 also easily synthesized by a solid state reaction of starting mixtures of different molar ratios of TiO 2 and Ti 2 O 3 . Ti 2 O 3 can be replaced by a variety of other trivalent metal oxides in this reaction. However, according to the current state of science and technology, there are only a few trivalent metal oxides in which the reaction products have the structure of Magnéli phases. These are in particular Cr 2 O 3 and V 2 O 3 .
  • modified titanium suboxides with the structure of Magnéli phases which are described by the general formula Ti n-2 Cr 2 O 2n-1 , with n ⁇ 4 can be produced easily .
  • Magnéli phases of the structure Ti n-2 Cr 2 O 2n-1 form with n ⁇ 4 in air.
  • Another way of making the phases is, as mentioned above, of P. Sujatha Devi, J. Solid State Chemistry, Vol. 110, 1994, p. 345-349 , described.
  • vanadium modified titanium suboxides with the structure of Magnéli phases described by the general formula Ti n-2 V 2 O 2n-1 with n ⁇ 3, for example according to the in US 5,049,537 simply produce these methods.
  • the toxicity of V 2 O 3 and other valence vanadium vanadium oxides requires increased precautions in the synthesis of the Magnéli phases, the preparation of the coating powders, and their processing by thermal spraying.
  • n in the formula Ti n-2 Me 2 O 2n-1 comprises a range of n ⁇ 2.
  • a narrower range of n ⁇ 1 can be achieved while adhering to narrower technological parameter limits during production.
  • n ⁇ 5 it is possible that only phases corresponding to a discrete value of n are present in the coating powder. This means that the coating powder is single-phase, if only one phase is known for n. If several phases are known for a discrete n, they may be present next to each other. Due to the ever smaller differences in the oxygen contents with increasing n, the coating powders with n ⁇ 5 can be prepared so that in addition to the desired phase n nor a second phase n + 1 or n-1 is present.
  • the coating powder for special requirements has a particle size in the range 10-45 microns.
  • the coating powders according to the invention can have different properties with respect to their porosity and their morphology, and the preparation can in principle be carried out in different ways.
  • the preferred variant consists in that the synthesis takes place via a solid-state reaction of homogeneous starting mixtures of finely dispersed titanium dioxide powder and trivalent metal oxide powder, in particular Cr 2 O 3 and V 2 O 3 of different molar ratios.
  • the homogeneous starting mixtures may contain the further alloying elements, for example in the form of oxides.
  • doping, metal powder or to Oxides decomposing compounds of the alloying metals can also be used.
  • an additional reduction can be carried out with a solid or gaseous reducing agent.
  • the suboxide Ti n-2 Me 2 O 2n-1 can optionally be processed by grinding processes and the grain size can be reduced.
  • the preparation of the coating powder from the synthesized powders of the composition Ti n-2 Me 2 O 2n-1 is preferably carried out by agglomeration, sintering and fractionation according to the in DE 100 00 979 described method steps, without changing the phase composition.
  • Spray drying is the preferred method for agglomeration.
  • the starting oxides TiO 2 and Cr 2 O 3 can be spray-dried together in the required ratio, and the corresponding Magnéli phases are obtained in the softened coating powder by reaction sintering.
  • Another possibility of production is to adjust the final phase composition during sintering of the coating powder from previously synthesized powders. This is done, for example, by changing the sintering temperature with respect to the synthesis temperature.
  • the grain size of the primary individual particles does not change or only slightly.
  • the grain size of the sintered individual particles in the coating powder particles is ⁇ 5 ⁇ m.
  • these coating powders are characterized inter alia by a spherical morphology and a porosity of greater than 3%, preferably greater than 10% ,
  • the porosity of the coating powders is determined by mercury porosimetry. When calculating the porosity, the intruded volume at a pressure corresponding to a pore diameter> 1 micron, is not taken into account, as this mercury in the Cavities between the individual coating powder particles is pressed. Due to the porosity and the fine individual particles, these coating powders are also characterized by specific surface areas> 1 m 2 / g.
  • coating powders according to the invention Another possibility for producing the coating powders according to the invention is that the synthesis of Ti n-2 Me 2 O 2n-1 is realized directly in the production of coating powders in other processes, for example melting and breaking or sintering and breaking. These coating powders can be easily further reduced with a gaseous reducing agent. The morphology, grain size and the particle size distribution of the starting powder are essentially retained. Thus, these coating powders may also have a different, for example, an angular morphology and have a porosity ⁇ 10%, preferably ⁇ 5%.
  • All coating powders according to the invention can be processed into layers with various surface technologies. They are particularly suitable for the process group of thermal spraying, such as, for example, plasma spraying, high-speed flame spraying (HVOF) and detonation spraying, and also laser and hybrid coating methods. No or only slight changes in the chemical phase composition are detectable in the layers relative to the coating powder. In particular, when using Ti n-2 Cr 2 O 2n-1 , there are no oxidation processes and thus changes in the chemical phase composition. The structure of the Magnéli phases can be transferred from the coating powder into the layer.
  • thermal spraying such as, for example, plasma spraying, high-speed flame spraying (HVOF) and detonation spraying, and also laser and hybrid coating methods.
  • HVOF high-speed flame spraying
  • detonation spraying laser and hybrid coating methods.
  • No or only slight changes in the chemical phase composition are detectable in the layers relative to the coating powder.
  • Ti n-2 Cr 2 O 2n-1 there are no oxidation processes and
  • the layers are preferably used as electrically conductive ceramic layers, which at the same time have high mechanical wear and corrosion resistance. In addition, they can also be used as solid-state lubricant and wear-resistant coatings. If the layers are made porous by the choice of suitable coating parameters, they are also suitable for use as electrode layers.
  • the suspension was treated simultaneously with 1.5% by weight of a matched binder of polyvinyl alcohol and polyethylene glycol and then prepared by spray-drying granules in a spherical form.
  • the debinding and sintering of the granules to the coating powder are carried out in a single-stage annealing in flat graphite crucibles under argon at a heating rate of 5 K / min to 600 ° C and 10 K / min to the sintering temperature of 1300 ° C with an isothermal holding time of 30 min ,
  • the sintered powders were subjected to gentle grinding.
  • the separation of the fraction> 45 .mu.m was carried out by sieving, the fraction ⁇ 10 .mu.m by air classification.
  • the fines content of the powder ⁇ 10 ⁇ m after fractionation was 4%.
  • the particle size distribution of the coating powder particles was measured by means of a laser diffraction meter by means of dry dispersion. The measurement revealed the granulometric characteristics d 10 of 15 ⁇ m, d 50 of 28 ⁇ m and d 90 of 43 ⁇ m.
  • the internal open porosity of the coating powder was determined to be 11% by means of mercury porosimetry. When calculating the porosity, the intruded volume was not taken into account at a pressure corresponding to a pore diameter> 1 ⁇ m, since this mercury is forced into the voids between the individual coating powder particles.
  • the specific surface area of the powder was 1.55 m 2 / g.
  • the coating powder was then subjected to atmospheric plasma spraying (APS) using an argon / hydrogen plasma with a power of 42 kW at gas flows of Ar 45 l / min; H 2 10 1 / min (each under standard conditions) applied to a steel substrate roughened by sandblasting immediately before spraying.
  • APS atmospheric plasma spraying
  • the spray distance was 110 mm and the powder delivery rate 35g / min. In this case, a layer thickness of 300 microns was achieved.
  • X-ray phase analysis were in the sprayed layer of Ti 2 Cr 2 O 7 detected.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Claims (13)

  1. Poudre pour revêtement à base de sous-oxydes de titane chimiquement modifiés avec des structures à défauts planaires des phases Magnéli, caractérisée en ce que la poudre est modifiée avec au moins un élément d'alliage métallique et est décrite par la formule générale Tin-2Me2O2n-1, Me étant Cr ou V et la poudre pour revêtement présente une granulométrie de l'ordre de 10 à 90 µm.
  2. Poudre pour revêtement selon la revendication 1, caractérisée en ce qu'elle contient un ou plusieurs autres éléments d'alliage.
  3. Poudre pour revêtement selon la revendication 1 ou 2, caractérisée en ce que, dans le cas où le premier élément d'alliage métallique est chrome, la composition de la poudre est décrite par la formule générale Tin-2Cr2O2n-1, avec n ≥ 4.
  4. Poudre pour revêtement selon la revendication 3, caractérisée en ce que, dans le cas où le premier élément d'alliage métallique est chrome, la composition de la poudre est décrite par la formule générale Tin-2Cr2O2n-1, avec n ≥ 3, cette composition est stabilisée par un autre élément d'alliage métallique.
  5. Poudre pour revêtement selon la revendication 1 ou 2, caractérisée en ce que, dans le cas où le premier élément d'alliage métallique est vanadium, la composition de la poudre est décrite par la formule générale Tin-2V2O2n-1, avec n ≥ 3.
  6. Poudre pour revêtement selon une ou plusieurs des revendications 1 à 5, caractérisée en ce que n est englobé dans une plage n ± 2.
  7. Poudre pour revêtement selon une ou plusieurs des revendications 1 à 5, caractérisée en ce que n est englobé dans une plage n ± 1.
  8. Poudre pour revêtement selon une ou plusieurs des revendications 1 à 5, caractérisée en ce qu'une seule phase est mise en évidence, phase qui corresponde à une valeur discrète de n, pour n < 5.
  9. Poudre pour revêtement selon une ou plusieurs des revendications 1 à 5, caractérisée en ce qu'on peut mettre en évidence deux phases si n ≥ 5.
  10. Poudre pour revêtement selon une ou plusieurs des revendications 1 à 9, caractérisée en ce qu'elle présente une granulométrie de l'ordre de 10 à 45 µm.
  11. Poudre pour revêtement selon une ou plusieurs des revendications 1 à 10, caractérisée en ce que la poudre de revêtement a une morphologie en forme de bille, présente une porosité ouverte supérieure à 3 % et est composée d'un ensemble de particules isolées frittées avec une granulométrie < 5 µm.
  12. Poudre pour revêtement selon la revendication 11, caractérisée en ce que la porosité ouverte de la poudre pour revêtement composée d'un ensemble de particules isolées frittées est supérieure à 10 %.
  13. Poudre pour revêtement selon une ou plusieurs des revendications 1 à 10, caractérisée en ce que la poudre de revêtement a une morphologie angulaire et présente une porosité inférieure à 10 %.
EP02740417A 2001-03-05 2002-03-04 Poudre de revetement a base de sous-oxydes de titane chimiquement modifies Expired - Lifetime EP1379708B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10110448 2001-03-05
DE10110448A DE10110448A1 (de) 2001-03-05 2001-03-05 Beschichtungspulver auf der Basis von chemisch modifizierten Titansuboxiden
PCT/EP2002/002323 WO2002079535A2 (fr) 2001-03-05 2002-03-04 Poudre de revetement a base de sous-oxydes de titane chimiquement modifies

Publications (2)

Publication Number Publication Date
EP1379708A2 EP1379708A2 (fr) 2004-01-14
EP1379708B1 true EP1379708B1 (fr) 2007-06-13

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EP02740417A Expired - Lifetime EP1379708B1 (fr) 2001-03-05 2002-03-04 Poudre de revetement a base de sous-oxydes de titane chimiquement modifies

Country Status (6)

Country Link
US (1) US7445763B2 (fr)
EP (1) EP1379708B1 (fr)
JP (1) JP4421820B2 (fr)
AT (1) ATE364733T1 (fr)
DE (3) DE10110448A1 (fr)
WO (1) WO2002079535A2 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004046320A1 (de) * 2004-09-17 2006-05-11 Bundesanstalt für Materialforschung und -Prüfung (BAM) Reibmaterialien/Tribowerkstoffe für radiale und axiale Folienlager
US20080112879A1 (en) * 2006-11-15 2008-05-15 Mccracken Colin G Production of high-purity titanium monoxide and capacitor production therefrom
US20080253958A1 (en) * 2006-11-15 2008-10-16 Mccracken Colin G Production of high-purity titanium monoxide and capacitor production therefrom
EP2099715A2 (fr) * 2007-01-11 2009-09-16 Ciba Holding Inc. Mélanges de pigments
DE102012107499A1 (de) * 2012-08-16 2014-05-22 Dr. Ing. H.C. F. Porsche Aktiengesellschaft Verfahren zur Beschichtung
US9672953B2 (en) * 2014-03-27 2017-06-06 EboNEXT Technologies (BVI) Devices and methods for advanced phase-locked materials
US9994785B2 (en) 2014-04-02 2018-06-12 Rolls-Royce Corporation Thermally stable self-lubricating coatings
CN112479702A (zh) * 2020-11-27 2021-03-12 安徽盈锐优材科技有限公司 一种等离子喷涂用氧化铬氧化钛复合粉末的制备方法

Family Cites Families (11)

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Publication number Priority date Publication date Assignee Title
US3816348A (en) * 1972-04-24 1974-06-11 Du Pont Compositions for stable low resistivity resistors
US4141743A (en) 1977-10-31 1979-02-27 Dresser Industries, Inc. Thermal spray powdered composite
US4977130A (en) * 1989-09-05 1990-12-11 Texaco Inc. Compositions involving V2 O3 -Al2 O3 -TiO2
US5049537A (en) * 1989-12-26 1991-09-17 Texaco Inc. Stable solid phases involving V2 O3 - TiO2 and mixtures of said phases
US5173215A (en) 1991-02-21 1992-12-22 Atraverda Limited Conductive titanium suboxide particulates
DE19511628C2 (de) 1995-03-30 2001-05-17 Walter Hunger Verfahren zum Beschichten einer Lauffläche einer Kolbenstange einer hydraulischen Kolben-Zylinder-Einheit
DE19651094C2 (de) * 1996-12-09 2002-01-31 Man Technologie Gmbh Tribosystem
FR2793812B1 (fr) * 1999-05-18 2001-08-17 Renault Piece mecanique de friction recouverte d'oxydes triboactifs stabilises par des oligoelements
FR2795095B1 (fr) 1999-06-16 2002-04-12 Renault Piece mecanique de friction recouverte d'oxydes triboactifs presentant un defaut de cations metalliques
DE10000979C1 (de) 1999-10-01 2001-05-10 Daimler Chrysler Ag Beschichtungspulver auf der Basis von Titansuboxiden
US6524750B1 (en) * 2000-06-17 2003-02-25 Eveready Battery Company, Inc. Doped titanium oxide additives

Also Published As

Publication number Publication date
US20040136898A1 (en) 2004-07-15
ATE364733T1 (de) 2007-07-15
JP2004524445A (ja) 2004-08-12
DE50210318D1 (de) 2007-07-26
DE10291362D2 (de) 2004-07-22
US7445763B2 (en) 2008-11-04
DE10110448A1 (de) 2002-09-19
WO2002079535A3 (fr) 2003-03-13
JP4421820B2 (ja) 2010-02-24
WO2002079535A2 (fr) 2002-10-10
EP1379708A2 (fr) 2004-01-14

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